RESUMO
We infer the swelling/de-swelling behavior of weakly ionizable poly(acrylic acid) (PAA) brushes of 2-39 kDa molar mass in the presence of KCl concentrations from 0.1-1000 mM, pH = 3, 7, and 9, and grafting densities σ = 0.12-2.15 chains per nm2 using a Quartz Crystal Microbalance with Dissipation (QCM-D), confirming and extending the work of Wu et al. to multiple chain lengths. At pH 7 and 9 (above the pKa â¼ 5), the brush initially swells at low KCl ionic strength (<10 mM) in the "osmotic brush" regime, and de-swells at higher salt concentrations, in the "salted brush" regime, and is relatively unaffected at pH 3, below the pKa, as expected. At pH 7, at low and moderate grafting densities, our results in the high-salt "salted brush" regime (Cs > 10 mM salt) agree with the predicted scaling H â¼ Nσ+1/3Cs-1/3 of brush height H, while in the low-salt "osmotic brush" regime (Cs < 10 mM salt), we find H â¼ Nσ+1/3Cs+0.28-0.38, whose dependence on Cs agrees with scaling theory for this regime, but the dependence on σ strongly disagrees with it. The predicted linearity in the degree of polymerization N is confirmed. The new results partially confirm scaling theory and clarify where improved theories and additional data are needed.